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Supporting Information Tailoring liquid crystal honeycombs by head-group choice

in bird-like bent-core mesogens

Ya-xin Li1,2, Huifang Cheng3, Xiangbing Zeng2, Yuan Tao3, Xiaohong Cheng*3,4 and Goran Ungar*1,2

1 State Key Laboratory for Mechanical Behaviour of Materials, Shaanxi International Research Center for Soft Materials, Xi’an Jiaotong University, Xi’an, PR China. 2 Department of Materials Sci. and Eng., University of Sheffield, Sheffield, UK 3 School of Chemical Science and Technology, Yunnan University, Kunming, PR China 4 School of Chemistry and Chemical Engineering, Yangtze Normal University, Fuling, PR China

Contents S1. Experimental methods ...................................................................................... 2 

S2. DSC results ........................................................................................................ 3 

S3. Additional POM images ..................................................................................... 5 

S4. Additional X-ray diffraction, SHG and molecular modelling/simulation results on individual compounds ........................................................................... 6 

S5. Estimation of number of molecules per columnar stratum ......................... 10 

S6. Electron densities of functional groups involved, non-bonded interaction energies and dipole moments of headgroups ..................................................... 11 

S7. Synthesis and analytical data ......................................................................... 12 

S8. NMR spectra ..................................................................................................... 16 

S9. References ....................................................................................................... 32 

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.This journal is © The Royal Society of Chemistry 2020

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S1. Experimental methods DSC thermograms were recorded on a DSC 200 F3 Maia calorimeter (NETZSCH) with heating/cooling rates as specified. Optical micrographs with crossed polarizers (POM) were recorded using an Olympus BX50 microscope equipped with a Mettler hot stage. Optical retardation was measured with a Berek compensator. A -plate was used to determine the direction of the optic axis. Grazing incidence X-ray scattering (GISAXS) experiments were carried out on beamline BM28 (XMaS) at European Synchrotron Radiation Facility (ESRF), France and I16 at Diamond Light Source, U.K. The X-ray energy was 12.0 keV, and 2d diffractograms were collected using a MAR165 CCD camera (ESRF) and Pilatus 2M detector (Diamond). Thin film samples were prepared from melt on silicon substrate. n-Tetracontane was used to calibrate the sample-to-detector distance. Powder SAXS and WAXS experiments were done at station I22 of Diamond Light Source. Powder samples were prepared in 1 mm glass capillaries and held in a modified Linkam hot stage. Pilatus 2M detector at a distance of 2.2 m from the sample was used. The X-ray energy was 12.4 keV. Electron density (ED) maps were calculated by inverse Fourier transformation using the standard procedure as described in International Tables for Crystallography. The structures p6mm and p2gg are centrosymmetric, thus the phase angle (ϕ) choices of the reflections are either 0 or π. However, this restriction does not apply to reflections (10) and (20) of the p3m1 phase and (11), (21), (22), (31) and (32) of the p31m phase. The selection of the maps is considered based on the physical and chemical information i.e. chemical structure, known electron densities of the molecular fragments, molecular models and simulation. Samples of ca. 50 μm thickness for Second Harmonic Generation (SHG) measurements were prepared on the rough side of silicon wafer and examined using a Zeiss LSM 510 Meta upright laser-scanning confocal microscope (Oberkochen, Germany) with a 40X/0.75NA objective. Temperature was controlled by a Mettler hot stage. A Chameleon Ti: Sapphire femtosecond pulsed laser (Coherent, California, USA) tuned to 800 nm, was attached to the microscope and focused onto the sample resulting in a SHG signal detectable at 400 nm. In order to exclude possible surface effects, first the beam was focused at the bottom of the LC film in contact with the Si substrate, then at 10 μm and 20 μm height, respectively. The SHG ratio was calculated by dividing the intensities at 400 nm by the averaged background signals around the peak. Molecular models were built using Materials Studio (Accelrys). Geometry optimization and molecular dynamic simulation were performed using the Forcite Plus module with Universal Force Field. The experimental value for a-parameter and the value for c from Table S7 were used. The convergence tolerances for geometry optimization were 1 cal/mol for energy and 0.5 kcal/mol/Å for force. Constant volume (NVT) annealing dynamics was performed through 30 cycles between 300 and 600 K with a total annealing time of 30 ps.

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S2. DSC results Table S1 Phase transition temperatures of the mesogenic compounds.

Compound

Rh-F/H a Rc a (asub) (Å) b T /°C [∆H/kJ mol-1] c

CO2CH3-F C6H12C4F9 29.8 ↑ Cr 55 Iso ↓ glass r.t. ↑ p3m1-reg 42 Iso d

Br-H CH2CH(C5H11)2 26.9 ↑ Cr1 78.7[8.9] Cr2 118.8[40.1] Iso ↓ 91.9[1.9] p3m1-

reg 32.2[8.6] Cr ↑ 113.7[33.3] Iso

CONH2-F C4H8C6F13 30.1 ↑ Cr 91.5[1.2] p3m1-reg 213.5[15.2] Iso ↓ 209.2[13.2]

p3m1-reg ↑ 212.5[13.3] Iso

CN-F C6H12C4F9 51.7 (29.8) ↑ Cr1 63[5.8] Cr2 73.3[4.2] p31m-sup 83.4[0.2] Iso ↓

77 (onset) p31m-sup ↑ 82.9[0.1] Iso

CN-H CH2CH(C5H11)2 24.5 ↑ Cr 112[16.9] Iso ↓ 81.5[1.6] p6mm-ran ↑ 84.4[1.6]

Iso

NO2-F C4H8C6F13 a 63.3 b 50.6 (29.2-31.7)

↑ Cr 85.7[0.7] p2gg 116.3[0.9] Iso ↓ 114[0.09] p2gg 109.9[1.5] ↑ p2gg-sup 117[2.0] Iso

aFirst part of compound name is the head group Rh, second part denotes the type of the attached chain. bLattice

parameter (subcell lattice parameter). For superlattice p31m, 𝑎 √ 𝑎. For superlattice p2gg, asub is in the

range of √ 𝑏 and 𝑎. cPeak DSC transition temperatures [and enthalpies] on 1st heating (↑), followed by cooling

(↓) and 2nd heating (↑), all at 10 K min-1. d Transition temperatures of CO2CH3-F are determined by XRD, SHG and POM. Phase abbreviations: Cr = crystal, p6mm-ran = hexagonal columnar phase with random orientation of the local 3-fold axis with 6-fold p6mm overall symmetry; p3m1-reg = columnar phase with trigonal symmetry and one column per unit cell; p31m-sup = trigonal superlattice with three columns per unit cell; p2gg-sup = rectangular superlattice with p2gg symmetry and four columns per cell; Iso = isotropic melt.

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Figure S1 DSC thermograms of compounds (a) Br-H at heating and cooling scan rate of 10 K min-1; (b) CONH2-F at heating and cooling scan rate of 10 K min-1; (c) CN-F at heating and cooling scan rate of 10 K min-1; (d) CN-H at heating and cooling scan rate of 10 K min-1; (e) NO2-F at heating and cooling scan rate of 10 K min-1.

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S3. Additional POM images

Figure S2 Polarized optical microscopy textures of (a, b) CN-H recorded at 70 °C (cooled from 100 °C), p6mm-ran = hexagonal columnar phase with p6mm symmetry and overall random packing; (c, d) CO2CH3-F recorded at 25 °C (cooled from 60 °C), p3m1-reg = the hexagonal columnar phase with three-fold symmetry and regular lattice; (e, f) Br-H recorded at 70 °C (cooled from 110 °C); (b, d and f) are recorded with a full-wave (λ) plate.

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S4. Additional X-ray diffraction, SHG and molecular modelling/simulation results of individual compounds S4.1. CO2CH3-F

Figure S3 (a) Powder SAXS curve and (b) GIWAXS/GISAXS pattern of CO2CH3-F recorded at 23 °C (cooled from isotropic temperature and kept at room temperature for 12 h to form liquid crystal phase); (c) reconstructed ED map (ϕ(10) = 20°, ϕ(11) = 0° and ϕ(20) = 300°) with schematic model overlaid; (b) Geometry optimized molecular model. Table S2 The indices, experimental, calculated d-spacings and relative integrated intensities of CO2CH3-F obtained from SAXS at 23 °C. All intensity values are Lorentz and multiplicity corrected.

(hk) d-spacing (Å) experimental

d-spacing (Å) calculated

Intensity Phase (°)

(10) 25.8 25.8 100.0 20 (11) 14.9 14.9 16.2 0 (20) 12.9 12.9 12.4 300

a = 29.8 Å

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Figure S4 Temperature dependent intensity of the second harmonic (400 nm) vs. background for 800 nm excitation of CO2CH3-F, generated at different heights. (The sample was heated to 60 °C, cooled to room temperature and kept for 12 h to form LC phase. Next, it was heated and examined every 5 °C.) S4.2. Br-H

Figure S5 (a) Powder SAXS curve and (b) GISAXS diffraction pattern of Br-H recorded at 70 °C (cooled from 110 °C). The position of the arrow in (a) supposed to show (20), but the intensity of (20) is too weak to be observed; (c) reconstructed electron density map (ϕ(10) = 20° and ϕ(11) = 0°), with schematic molecules overlaid; (d) snapshot of dynamic simulation.

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Table S3 The indices, experimental, calculated d-spacings and relative integrated intensities of Br-H obtained from SAXS at 70 °C (cooled from 110 °C). All intensity values are Lorentz and multiplicity corrected.

(hk) d-spacing (Å) experimental

d-spacing (Å) calculated

Intensity Phase (°)

(10) 23.3 23.3 26.3 20 (11) 13.5 13.5 100.0 0

a = 26.9 Å

Figure S6 Temperature dependent intensity of the second harmonic (400 nm) vs. background for 800 nm excitation of Br-H, generated at different heights (cooled from 130 to 50 °C). S4.3. CONH2-F Table S4 The indices, experimental, calculated d-spacings and relative integrated intensities of CONH2-F obtained from SAXS at 130 °C (cooled from 230 °C). All intensity values are Lorentz and multiplicity corrected.

(hk) d-spacing (Å) experimental

d-spacing (Å) calculated

Intensity Phase (°)

(10) 26.1 26.1 100.0 20 (11) 15.1 15.1 50.8 0 (20) 13.1 13.1 8.45 140

a = 30.1 Å

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Figure S7 Temperature dependent intensity of the second harmonic (400 nm) vs. background for 800 nm excitation of CONH2-F, generated at different heights (heated from 170 to 230 °C). S4.4. CN-F Table S5 The indices, experimental, calculated d-spacings, relative integrated intensities and phases of CN-F recorded at 70 °C (cooled from 90 °C) from SAXS. All intensities values are Lorentz and multiplicity corrected.

(hk) d-spacing

experimental (Å) d-spacing

calculated (Å) Intensity Phase (°)

(10) 44.9 44.8 0.2 0 (11) 25.9 25.9 90.8 20 (20) 22.4 22.4 0.1 0 (21) 16.9 16.9 13.7 240 (30) 14.9 14.9 46.6 0 (22) 12.9 12.9 3.6 20 (31) 12.4 12.4 6.5 220 (40) 11.2 11.2 1.0 180 (32) 10.2 10.3 100.0 60

a = 51.7 Å

S4.5. CN-H Table S6 The indices, experimental, calculated d-spacings and relative integrated intensities of CN-H obtained from SAXS at 70 °C (cooled from 100 °C). All intensity values are Lorentz and multiplicity corrected.

(hk) d-spacing (Å) experimental

d-spacing (Å) calculated

Intensity Phase

(10) 21.2 21.2 25.4 π (11) 12.2 12.2 100.0 π (20) 10.6 10.6 8.2 π

a = 24.5 Å

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Figure S8 Temperature dependent intensity of the second harmonic (400 nm) vs. background for 800 nm excitation of CN-H, generated at different heights (cooling from 110 °C to 30 °C). S4.6. NO2-F Table S7 The experimental, calculated d-spacings, intensities, phases and lattice parameters of the Colrec/p2gg phase observed from SAXS at 100 °C. All intensity values are Lorentz and multiplicity corrected.

(hk) d-spacing (Å) experimental

d-spacing (Å) calculated

Intensity Phase

(11) 39.5 39.5 1.9 0 (20) 31.6 31.7 11.6 0 (21) 26.9 26.8 86.6 0 (02) 25.2 25.3 100.0 π (12) 23.4 23.5 0.6 π (22) 19.8 19.8 2.0 0 (31) 19.5 19.5 0.8 π (13) 16.3 16.3 1.2 0 (32) 16.2 16.2 1.2 0 (40) 15.8 15.8 5.1 - (41) 15.1 15.1 0.5 - (23) 14.9 14.9 11.1 -

a = 63.3 Å, b = 50.6 Å

S5. Estimation of number of molecules per columnar stratum Table S8 Estimation of number of molecules per column stratum

Sample Rc Plane group a (Å) c (Å)a Vcell (Å3)b Vmol (Å3)c nCrd nliq

e navef

CO2CH3-F C6H12C4F9 p3m1-reg 29.8 4.3 3306.9 980.4 3.4 2.7 3.0 Br-H CH2CH(C5H11)2 p3m1-reg 26.9 5.0 3133.2 941.3 3.3 2.6 3.0

CONH2-F C4H8C6F13 p3m1-reg 30.1 4.2 3318.9 984.1 3.4 2.6 3.0 CN-F C6H12C4F9 p31m-reg 51.7 4.1 9490.4 943.1 10.1 7.9 9.0 CN-H CH2CH(C5H11)2 p6mm-ran 24.5 6.0 3118.9 939.6 3.3 2.6 3.0

NO2-F C4H8C6F13 p2gg-sup a 63.3 b 50.6

4.0 12940.0 961.0 13.5 10.5 12.0

a: Thickness of column stratum, or average spacing between molecules along column axis, c, is adjusted to obtain an integer value of nave. b: Volume of the unit cell for hexagonal phase Vcell = a2*0.866*c, and rectangular phase Vcell = a*b*c; c: Volume of molecule (Vmol) = volume of a single molecule as calculated using the crystal volume increments[S1]; d: nCr = Vcell/Vmol; e: nliq = 0.55/0.7*nCr (average packing coefficient in the crystal is k = 0.7, in isotropic liquid k = 0.55) [S2]; f: nave = (nCr + nliq)/2.

Table S9 Comparison of lattice parameters and column areas of honeycomb phases, including that of the previously reported anchor-shaped molecule 2b with Rh = H [S3].

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Name Plane group Lattice parameters (Å) Column area A (Å2)* CN-H p6mm-ran 24.5 519.8 Br-H p3m1-reg 26.9 626.7

CO2CH3-F p3m1-reg 29.8 769.1 CN-F p31m -sup 51.7 771.6

CONH2-F p3m1-reg 30.1 784.6 NO2-F p2gg-sup a = 63.3 b = 50.6 800.7 2b[S3] p3m1-reg 28.8 718.3

*The column area of the regular lattices is calculated by 𝐴 √ 𝑎 . For the superlattices p31m (CN-F) and p2gg

(NO2-F), there are 3 and 4 columns in each unit cell, respectively. The column area of p31m-sup is √ 𝑎 and that

of p2gg-sup is .

S6. Electron densities of functional groups involved, non-bonded interaction energies and dipole moments of headgroups Table S10 Electron densities of different functional groups involved a.

a Volume of relevant part of molecule is calculated using the method of crystal increments [S1]. Table S11 Hydrogen bond enthalpies and dipole moments of glycerol and headgroups. Functional Group

H-bond enthalpy between head group and Csp3-OH (-kcal/mol)

Enthalpy of non-bonded interaction among headgroups (-kcal/mol)

Dipole moment of headgroup (D)

Glycerol 4.8 (single intermolecular H-bond between glycerols)[S4] - Br 0.7 (n-heptyl bromide with n-propanol

[S5]) 1.0 (bromoform, dipolar) [S5]

1.72 (bromobenzene [S6])

CONH2 4.5 (acetamide with isopropanol [S5]) 7.1 (formamide, H-bond) [S7]

-

CN 3.1 (benzonitrile with water, similar to benzonitrile with alcohols [S8])

3.1 (Benzonitrile, dipolar)

[S8]

4.48 (benzonitrile [S9])

NO2 2.8 (nitromethane with methanol [S10])

3.1 (non-bonding between Onitro and π(N)nitro

[S11]) 4.22 (nitrobenzene[S12])

COOCH3 2.3 (thienylacryloyl methyl ester with ethanol[S13]) 2.5 (5-methylthienylacryloyl methyl ester with ethanol[S13])

- 1.75 (methyl acetate [S14])

Compound Aromatic core (105 electron/Å3)

glycerol groups (105 electron/Å3)

head group (105 electron/Å3)

Aliphatic chain 1 (105 electron/Å3)

Fluorinated chain (105 electron/Å3)

CONH2-F

4.38 4.50

4.72 (-CONH2) 3.69 (-OC4H8) 6.58 (-C6F13) Br-H 10.60 (-Br) 3.35 (-O-CH2-

(C5H12)2) -

CO2CH3-F 4.52 (-COOCH3) 3.54 (-OC6H12) 6.60 (-C4F9) CN-F 4.15 (-CN) 3.54 (-OC6H12) 6.60 (-C4F9) CN-H 41.5 (-CN) 3.35 (-O-CH2-

(C5H12)2) -

NO2-F 6.39 (-NO2) 3.69 (-OC4H8) 6.58 (-C6F13)

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S7. Synthesis and analytical data General Remarks Reactions requiring an inert gas atmosphere were conducted under argon and the glassware was oven-dried (140 °C). Commercially available chemicals were used as received. 1H NMR and 13C NMR spectra were recorded on a Bruker–DRX-500 spectrometer. Elemental analysis was performed using an Elementar VARIO EL elemental analyzer. HRMS were performed on LTQ Orbitrap XL. Column chromatography was performed with merck silica gel 60 (230-400 mesh).

Scheme 1 : Synthesis of bent shaped bola amphiphilies, reagents and conditions: (i) I2, KI, ammonia, MeOH, 25 oC, 2 h, 52%; (ii) R-Br (R = C14H29 or (CH2)nCmF2m+1

[S15]), K2CO3, CH3CN, reflux, 20 h; (iii) Dihydrogenperoxide, sodium hydroxide inethanol, water, T= 60 °C[S16], 1 h; (iv) 2-methylbut-3-yn-2-ol, THF, Et3N, Pd(PPh3)4, CuI, RT, 89%; (v) KOH, toluene, 100 °C, 15 h, 88%; (vi) THF, Et3N, Pd(PPh3)4, CuI, RT, 64-88%; (vii) PPTS, CH3OH, RT, 15 h, 77-87%. General procedure for the synthesis of compounds 2 [16]

A solution of 4-X 15.0 mmol in 20 % ammonium hydroxide (12 mL) and methanol (6 mL) was stirred vigorously as a suspension of I2 (30.0 mmol) and KI (60.0 mmol) in H2O (15 mL) was added dropwise. The solution was stirred for 2 h at RT. The mixture was extracted with ethyl acetate (3×40 mL). The combined organic phase was washed with brine dried over Na2SO4, and the solvent was removed in vacuo. The residue was purified by recrystallization (Ethanol). 2a: 4-hydroxy-3,5-diiodobenzonitrile: Yield 66%, yellow crystal. 1H NMR (400 MHz, CDCl3), δ(ppm): 7.96 (s, 2 H, 2 ArH), 6.23 (s, 1 H, OH).

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2b: 2,6-diiodo-4-nitrophenol: Yield 51%, yellow crystal. 1H NMR (400 MHz, CDCl3), δ(ppm): 8.59 (s, 2 H, 2 ArH), 6.36 (s, 1 H, OH). 2c: 2,6-diiodo-4-bromophenol : Yield 61%, white crystal. 1H NMR (400 MHz, CDCl3), δ(ppm): 7.87 (s, 2 H, 2 ArH), 6.23 (s, 1 H, OH). 2d: Methyl-4-hydroxy-3,5-diiodobenzoate: Yield 59%, light yellow crystal. 1HNMR (400 MHz, CDCl3), δ(ppm): 8.36 (s, 2 H, 2ArH), 6.13 (s, 1 H, OH), 3.89 (s, 3 H, COOCH3). General procedure for the synthesis of compounds 3 A mixture of 0.4 mmol 2, 0.4 mmol corresponding bromoalkane, 3.6 mmol K2CO3 and 20 ml MeCN is stirred for 20 hours under reflux. Water is then added and the mixture is extracted three times with Et2O. The combined organic phases are washed with brine, dried over anhydrous Na2SO4 and evaporated under reduced pressure. The crude product is purified by column chromatography on silica gel (eluent: PE). 3a-H: 3,5-diiodo-4-(tetradecyloxy)benzonitrile: Yield 90%, colorless oil, 485.1 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 8.05 (s, 2 H, 2 ArH), 3.89-3.87 (d, 2 H, J = 6.4 Hz, OCH2), 2.04-2.00 (m, 1 H, CH), 1.59-1.54 (m, 2 H, CH2), 1.47-1.38 (m, 4 H, 2 CH2), 1.37-1.26 (m, 10 H, 5 CH2), 0.92-0.89 (t, 6 H, J = 6.8 Hz, 2 CH3). 3a-F: 3,5-diiodo-4-(7,7,8,8,9,9,10,10,10-nonafluorodeyloxy)benzonitrile: Yield: 84%, white solid, 565.2 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 8.05 (s, 2 H, 2 ArH), 4.02 (t, 3J(H,H) = 6.4 Hz, 2 H, ArOCH2), 2.03 - 2.14 (m, 2 H, CH2CF2), 1.92- 1.99 (q, 3J(H,H) = 7.0 Hz, 2 H, OCH2CH2), 1.60 - 1.72 (m, 4 H, 2 CH2), 1.42 - 1.46 (m, 2 H, CH2). 3b-F: 1,3-diiodo-5-nitro-2-(5,5,6,6,7,7,8,8,9,9,10,10,10-nonafluorodeyloxy)benzene: Yield: 68%, yellow solid, 520.1 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 8.65 (s, 2 H, 2 ArH), 4.11-4.08 (t, 2 H, J = 6.4 Hz, OCH2), 2.36-2.21 (m, 2 H, CH2), 2.07-1.93 (m, 4 H, 2 CH2). 3c-H: 1,3-diiodo-5-bromo-2-(tetradecyloxy)benzene: Yield 94%, colorless oil, 556.4 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 7.88 (s, 2 H, 2 ArH), 3.82-3.80 (d, 2 H, J = 6.0 Hz, OCH2), 2.00-1.97 (t, 1 H, J = 6.6 Hz, CH), 1.58-1.52 (m, 2 H, CH2), 1.42-1.38 (m, 4 H, 2 CH2), 1.45-1.36 (m, 10 H, 5 CH2), 0.92-0.89 (t, 6 H, J = 6.8 Hz, 2 CH3). 3d-F: 3,5-diiodo-5-methyl-4-(7,7,8,8,9,9,10,10,10-nonafluoroyloxy)benzoate: Yield 83%, white solid, 589.1 mg. 1H-NMR (400 MHz, CDCl3), δ(ppm): 8.32 (s, 2 H, 2ArH), 4.03-4.00 (t, 2 H, J = 6.4 Hz, OCH2), 3.86 (s, 3 H, COOCH3), 2.13-2.02 (m, 2 H, CH2), 1.97-1.86 (m, 2 H, CH2), 1.71-1.53 (m, 4 H, 2 CH2), 1.52-1.42 (m, 2 H, CH2). General procedure for the synthesis of compounds 4 [S17] A mixture of 3,5-diiodobenzonitrile 3 and 5.0 mmol NaOH was dissolved in 10 ml of ethanol solution, and then H2O2 was added for 15 drops, and refluxed at 78 °C for 4 h. After the reaction, ethyl acetate (3 × 30 mL) was added to the mixture, and the extracted organic layers were combined and washed with saturated brine (2 ×20 mL), dried over anhydrous MgSO4, and evaporated under reduced pressure. The crude product is purified by column chromatography on silica gel (petroleum ether: ethyl acetate = 5: 1). 4-F: 3,5-diiodo-5-formamide-4-(5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro-10-deca-5,7,9-triyn-1-yloxy)benzamide: Yield 80%, white solid, 610.3 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 8.21 (s, 2 H, 2 ArH), 6.08-5.52 (m, 2 H, NH2), 4.06-4.03 (t, 2 H, J = 6.4 Hz, OCH2), 2.32-2.18 (m, 2 H, CH2), 2.07-1.93 (m, 4 H, 2 CH2).

S14

General procedure for the synthesis of compounds 8 by Sonogashira coupling [S17] The appropriate 3 or 4 (0.5 mmol) and 4-(4-ethynylphenoxymethyl)-2,2-dimethyl-1,3-dioxolane 7[S3, 18 ] (1.2 mmol) were dissolved in a mixture of dry THF (7 mL) and dry triethylamine (5 mL) under a nitrogen atmosphere. Then a mixture of Pd(PPh3)4 (0.05 mmol), CuI (0.12 mmol) was added, and the solution was stirred for overnight at RT. Ethyl acetate (30 mL) was added into the mixture, and washed with water (3×10 mL) and brine (3×10 mL), the organic layer were separated and dried over anhydrous Na2SO4, and the solvent was evaporated in vacuo. The residue was purified by column chromatography (petroleum ether : ethyl acetate : chloroform = 10:1:1). CN-H-4CH3: Yield 75%, red-brown solid, 224.2 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 8.03 (s, 2 H, 2 ArH), 7.49-7.45 (m, 4 H, 4 ArH), 6.90-6.88 (d, J = 8.8 Hz, 4 H, 4 ArH), 4.52-4.46 (m, 2 H, 2 OCH), 4.20-4.16 (m, 4 H, 2 ArOCH2), 4.09-4.05 (m, 2 H, ArOCH2CH), 3.98-3.95 (m, 2 H, OCH2), 3.93-3.89 (m, 2 H, ArOCH2CH), 1.83-1.80 (t, 1 H, J = 6.0 Hz, ArOCH2CH), 1.60-1.54 (m, 6 H, 3 CH2), 1.47 (s, 6 H, 2 CH3), 1.41 (s, 6 H, 2 CH3), 1.38-1.17 (m, 12 H, 6 CH2), 0.82-0.78 (t, J = 6.8 Hz, 6 H, 2 CH3). CN-F-4CH3: Yield 76%, red-brown solid, 267.9 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 7.71 (s, 2 H, 2 ArH), 7.48-7.46 (d, J = 8.8 Hz, 4 H, 4 ArH), 6.94-6.92 (d, J = 8.8 Hz, 4 H, 4 ArH), 4.53-4.48 (m, 2 H, OCH), 4.46-4.43 (t, J = 6.0 Hz, 2 H, ArOCH2CH2), 4.22-4.17 (m, 2 H, ArOCH2CH), 4.11-4.06 (m, 2 H, OCH2), 4.01-3.94 (m, 2 H, ArOCH2CH), 3.93-3.91 (m, 2 H, OCH2), 2.00-1.96 (m, 2 H, CH2CF2), 1.93-1.86 (m, 2 H, OCH2CH2) 1.68-1.60 (m, 2 H, CH2), 1.57-1.50 (m, 2 H, CH2), 1.49 (s, 6 H, 2 CH3), 1.43 (s, 6 H, 2 CH3), 1.32-1.23 (m, 2 H, CH2). NO2-F-4CH3: Yield 51%, brown-yellow solid, 198.5 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 8.28 (s, 2 H, 2 ArH), 7.48-7.44 (m, 4 H, 4 ArH), 6.88-6.85 (d, J = 8.8 Hz, 4 H, 4 ArH), 4.51-4.46 (m, 4 H, 2 OCH2, ArOCH2CH2), 4.20-4.17 (m, 2 H, ArOCH2CH), 4.09-4.04 (m, 2 H, OCH2), 3.99-3.95 (m, 2 H, ArOCH2CH), 3.94-3.88 (m, 2 H, OCH2), 1.99-1.96 (m, 2 H, CH2CF2), 1.94-1.89 (m, 2 H, OCH2CH2), 1.75-1.64 (m, 2 H, CH2), 1.47 (s, 6 H, 2 CH3), 1.41 (s, 6 H, 2 CH3). Br-H-4CH3: Yield 79%, red-brown solid, 252.9 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 7.53 (s, 2 H, 2 ArH), 7.46-7.43 (m, 4 H, 4 ArH), 6.90-6.88 (d, J = 8.8 Hz, 4 H, 4 ArH), 4.52-4.46 (m, 2 H, 2 OCH), 4.20-4.16 (m, 4 H, 2 ArOCH2), 4.09-4.05 (m, 2 H, ArOCH2CH), 3.98-3.95 (m, 2 H, OCH2), 3.93-3.89 (m, 2 H, ArOCH2CH), 1.83-1.80 (t, 1 H, J = 6.0 Hz, ArOCH2CH), 1.60-1.54 (m, 6 H, 3 CH2), 1.47 (s, 6 H, 2 CH3), 1.41 (s, 6 H, 2 CH3), 1.38-1.17 (m, 12 H, 6 CH2), 0.82-0.78 (t, J = 6.8 Hz, 6 H, 2 CH3). COOCH3-F-4CH3: Yield 82%, red-brown solid, 299.9 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 8.10 (s, 2 H, 2 ArH), 7.47-7.44 (d, J = 8.8 Hz, 4 H, 4 ArH), 6.92-6.89 (d, J = 8.8 Hz, 4 H, 4 ArH), 4.50-4.46 (m, 2 H, OCH2), 4.44-4.41(t, J = 6.0 Hz, 2 H, ArOCH2CH2), 4.20-4.16 (m, 2 H, ArOCH2CH), 4.09-4.05 (m, 2 H, OCH2), 3.98-3.94 (m, 2 H, ArOCH2CH), 3.92-3.89 (m, 2 H, OCH2), 1.98-1.85 (m, 2H, CH2CF2), 1.68-1.63 (m, 2 H, OCH2CH2) , 1.62-1.49 (m, 6 H 3 CH2), 1.47 (s, 6 H, 2 CH3), 1.41 (s, 6 H, 2 CH3). CONH2-F-4CH3: Yield 63%, red-brown solid, 244.8 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 7.89 (s, 2 H, 2 ArH), 7.46-7.44 (d, J = 8.8 Hz, 4 H, 4 ArH), 6.91-6.89 (d, J = 8.8 Hz, 4 H, 4 ArH), 4.52-4.46 (m, 2 H, OCH), 4.44-4.41(t, J = 6.0 Hz, 2 H, ArOCH2CH2), 4.20-4.16 (m, 2 H, ArOCH2CH), 4.09-4.05 (m, 2 H, OCH2), 3.99-3.95 (m, 2 H, ArOCH2CH), 3.92-3.89 (m, 2 H, OCH2), 1.98-1.85 (m, 2 H, CH2CF2), 1.68-1.63 (m, 2 H, OCH2CH2), 1.62-1.49 (m, 2 H, CH2), 1.47 (s, 6 H, 2 CH3), 1.41 (s, 6 H, 2 CH3). General procedure for the synthesis of compounds 9 [S3,18]

S15

8 (0.5 mmol) was dissolved in CH3OH (30 mL) and PPTS (120 mg) was added. The mixture was refluxed for 12 h, then cooled to RT, and extracted with chloroform (3×30 mL). The combined extracts were washed with aqueous saturated NaHCO3 solution (3×30 mL) and H2O (3×30 mL), dried over anhydrous Na2SO4, then the solvent was removed in vacuo. The residue was purified by column chromatography (petroleum ether : acetone = 3 : 2). CN-H: Yeild 71%, white solid, 142.2 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 7.66 (s, 2 H, 2 ArH), 7.47-7.44 (m, 4 H, 4 ArH), 6.92-6.89 (t, J = 7.2 Hz, 4 H, 4 ArH ), 4.37-4.35 (d, 2 H, J = 5.2 Hz, ArOCH2CH2), 4.15-4.12 (m, 2 H, 2 CHOH), 4.08-4.06 (t, 4 H, J = 3.2 Hz, 2 ArOCH2CH), 3.88-3.84 (m, 2 H, CH2OH), 3.78-3.74 (m, 2 H, CH2OH), 1.85-1.79 (m, 1 H, ArOCH2CH), 1.62-1.53 (m, 2 H, CH2), 1.46-1.27 (m, 6 H, 3 CH2), 1.23-1.13 (m, 8 H, 4 CH2), 0.88-0.86 (t, 6 H, J = 6.3, 2 CH3). 13C NMR (100 MHz, CDCl3), δ (ppm): 163.97(1C), 158.94(2C), 136.39(2C), 133.17(4C), 118.59(2C), 117.66(1C), 115.26(2C), 114.66(4C), 106.76(1C), 95.62(2C), 82.86(2C), 70.24(4C), 69.19(4C), 63.51(4C), 39.36, 32.22, 31.09, 26.71, 22.62, 14.10(multi carbons in alkyl chain); elemental analysis calcd (%) for C41H49NO7 (667.84): C 73.74, H 7.40, N 2.10; found: C 73.53, H 7.19, N 1.90. HRMS (ESI): m/z calcd for C41H49NO7Na [M + Na]+ 690.34, found 690.34. CN-F: Yeild 62%, white solid,149.0 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 7.70 (s, 2 H, 2 ArH), 7.49-7.47 (d, 4 H, J = 8.4 Hz, 4 ArH), 6.95-6.92 (d, 4 H, J = 8.8 Hz, 4 ArH), 4.46-4.43 (t, 2 H, J = 6.0 Hz, ArOCH2CH2), 4.16-4.13 (t, 2 H, J = 6.8 Hz, CHOH), 4.11-4.08 (t, 2 H, J = 5.4 Hz, ArOCH2CH), 3.90-3.86 (m, 2 H, CH2OH), 3.80-3.76 (m, 2 H, CH2OH), 2.20 (s, 4 H, 2 CH2OH, 2 CHOH), 2.00-1.88 (m, 4 H, ArOCH2CH2CH2), 1.67-1.63 (m, 2 H, CH2), 1.57-1.53 (m, 2 H, CH2), 1.47-1.42 (m, 2 H, CH2). 13C NMR (100 MHz, CDCl3), δ (ppm): 163.67(1C), 159.06(2C), 136.18(2C), 133.15(4C), 119.15(2C), 117.56(2C), 115.09(2C), 114.72(4C), 107.32(1C), 95.68(2C), 82.58(2C), 74.30(2C), 70.24 (2C), 69.16(2C), 63.48(2C), 30.87(1C), 30.65, 30.43, 30.26, 28.98, 25.98, 20.08(multi carbons in alkyl chain); elemental analysis calcd (%) for C39H36F9NO7 (801.70): C 58.43, H 4.53, N 1.75; found: C 58.21, H 4.37, N 1.53. HRMS (ESI): m/z calcd for C39H36F9NO7Na [M + Na]+ 824.22, found 824.22. NO2-F: Yield: 64%, yellow solid, 171.5 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 8.28 (s, 2 H,2 ArH), 7.48-7.46 (d, 4 H, J = 8.4 Hz, 4 ArH), 6.93-6.91 (d, 4 H, J = 8.4 Hz, 4 ArH ), 4.51 (s, 2 H, ArOCH2CH2), 4.14 (s, 2 H, CH2OH), 4.08-4.07 (d, 2 H, J = 4.0 Hz, ArOCH2CH), 3.88-3.85 (m, 2 H, CH2OH), 3.78-3.75 (m, 2 H, CH2OH), 2.61 (s, 2 H, 2 CH2OH), 2.14 (m, 2 H, CH2), 2.09 (s, 2 H, 2 CHOH), 2.02-1.97 (m, 4 H, 2 CH2). 13C NMR (100 MHz, CDCl3), δ (ppm): 164.42 (1C), 159.40(2C), 142.57 (2C), 132.86(2C), 127.53 (2C), 118.27(1C), 114.60(6C), 113.96(2C), 95.94(2C), 82.12(2C), 73.48(1C), 70.10(2C), 68.98(2C), 63.31(2C), 40.46, 40.25, 40.04, 39.83, 39.62, 39.42, 39.20, 30.36, 29.67, 29.40, 17.14(multi carbons in alkyl chain); elemental analysis calcd (%) for C38H32F13NO9 (893.65): C 51.07, H 3.61, N 1.57; found: C 49.82, H 3.42, N 1.39. HRMS (ESI): m/z calcd for C38H32F13NO9Na [M + Na]+ 916.18, found 916.18. Br-H: Yeild 72%, white solid, 155.6 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 7.53 (s, 2 H, 2 ArH), 7.47-7.43 (m, 4 H, 4 ArH), 6.91-6.88 (m, 4 H, 4 ArH ), 4.22-4.19 (m, 2 H, ArOCH2CH2), 4.17-4.12 (m, 2 H, CHOH), 4.11-4.06 (m, 4 H, 2 ArOCH2CH), 3.88-3.84 (m, 2 H, CH2OH), 3.78-3.74 (m, 2 H, CH2OH), 1.83-1.80 (t, 1 H, J = 6.0 Hz, ArOCH2CH), 1.63-1.54 (m, 2 H, CH2), 1.42-1.28 (m, 6 H, 3 CH2), 1.24-1.15 (m, 8 H, 4 CH2), 0.88-0.86 (t, 6 H, J = 6.3, 2 CH3). 13C NMR (100 MHz, CDCl3), δ (ppm): 160.32(1C), 158.87(2C), 135.61(2C), 133.30(4C), 119.67(2C), 115.89(2C), 115.06(1C), 114.75(4C), 94.79(2C), 83.61(2C), 70.43(4C), 69.36(4C), 63.70(4C), 39.57, 32.42, 31.41, 26.96, 22.78, 14.25(multi carbons in alkyl chain); elemental analysis calcd (%) for C40H49BrO7 (721.73) : C 66.57, H 6.84; found: C 66.34, H 6.64. HRMS (ESI): m/z calcd for C40H49BrO7Na [M + Na]+ 743.26, found 743.26. COOCH3-F: Yield 74%, white solid, 185.2 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 8.09 (s, 2 H, 2 ArH), 7.46-7.44 (d, 4 H, J = 8.8 Hz, 4 ArH), 6.90-6.88 (d, 4 H, J = 8.8 Hz, 4 ArH ), 4.43-4.40 (t, 2 H, J = 6.0 Hz, ArOCH2CH2), 4.14-4.11 (m, 2 H, ArOCH2CH), 4.07-4.02 (m, 4 H,

S16

ArOCH2CH, CH2OH), 3.91 (s, 3 H, COOCH3), 3.87-3.83 (m, 2 H, CH2OH), 3.76-3.73 (m, 2 H, CH2OH), 2.89-2.61 (m, 4 H, 2 CH2OH, 2 CHOH), 1.97-1.84 (m, 4 H, 2 CH2), 1.67-1.60 (m, 2 H, CH2), 1.54-1.48 (m, 2 H, CH2), 1.44-1.37 (m, 2 H, CH2). 13C NMR (100 MHz, CDCl3), δ (ppm): 165.81(1C), 164.07(1C), 158.91(2C), 134.64(2C), 133.19(4C), 125.38(1C), 117.93(2C), 115.84(2C), 114.80(4C), 94.37(2C), 83.92(2C), 74.19(2C), 70.46 (2C), 69.30(2C), 63.67(2C), 31.04, 30.82, 30.59, 30.44, 26.15, 20.23(multi carbons in alkyl chain); elemental analysis calcd (%) for C40H39F9O9 (834.73): C 57.56, H 4.71; found: C 57.32, H 4.46. HRMS (ESI): m/z calcd for C40H39F9O9Na [M + Na]+ 857.23, found 857.23.

CONH2-F: Yield 57%, white solid, 148.4 mg. 1H NMR (400 MHz, CDCl3), δ(ppm): 7.87 (s, 2 H, 2 ArH), 7.39-7.37 (d, 4 H, J = 8.4 Hz, 4 ArH), 6.86-6.84 (d, 4 H, J = 8.8 Hz, 4 ArH ), 4.35-4.32 (t, 2 H, J = 6.0 Hz, ArOCH2CH2), 4.00-3.95 (m, 6 H, 3 CH2), 3.73-3.69 (m, 2 H, CH2), 3.66-3.62 (m, 2 H, CH2), 1.99-1.90 (m, 2 H, CH2), 1.85-1.80 (m, 2 H, CH2), 1.62-1.55 (m, 2 H, CH2), 1.53-1.45 (m, 2 H, CH2), 1.41-1.37 (m, 2 H, CH2). 13C NMR (100 MHz, CDCl3), δ (ppm): 168.78(1C), 162.91(1C), 159.05(2C), 132.82(6C), 132.26(2C), 128.30(1C), 117.87(2C), 115.10(2C), 114.55(6C), 94.34(2C), 83.45(2C), 74.03(1C), 70.23(2C), 68.90(2C), 63.19(2C), 30.71, 30.49, 30.27, 30.11, 28.83, 25.85, 19.93(multi carbons in alkyl chain); elemental analysis calcd (%) for C39H34F13NO8 (891.68): C 52.53, H 3.84, N 1.57; found: C 52.34, H 3.62, N 1.38. HRMS (ESI): m/z calcd for C39H34F13NO8Na [M + Na]+ 914.20, found 914.20.

S8. NMR spectra 1H and 13C NMR spectra for representive compounds

S17

NO2

I I

OH

S18

Figure S9 1H NMR (CDCl3, 400 MHz, ppm) spectra of compounds 4-Rh-2,6-diiodophenol (Rh= CN, NO2, Br, COOCH3).

S19

S20

CONH2

I I

O

C6F13

S21

Figure S10 1H NMR (CDCl3, 400 MHz, ppm) spectra of compounds 3 and 4.

CN

O

OOOO O

O

C4F9

S22

Br

O

C5H11C5H11OOO

O OO

NO2

O

OOOO O

O

C6F13

S23

Figure S11 1H NMR (CDCl3, 400 MHz, ppm) spectra of compounds 8

S24

S25

S26

Figure S12 1H NMR (CDCl3, 400 MHz, ppm) spectra of compounds Br-H, CN-H, CN-F, NO2-F, CONH2-F, COOCH3-F.

S27

CN

O

OOHOHO OH

OH

C4F9

S28

Br

O

C5H11C5H11OOHO

HO OHOH

S29

S30

Figure S13 13C NMR (CDCl3, 400 MHz, ppm) spectra of compounds Br-H, CN-H, CN-F, NO2-F, CONH2-F, COOCH3-F. HRMS (ESI) for representive final compounds 9

S31

S32

Figure S14 HRMS (ESI) results for the final compounds.

S9. References [S1] A. Immirzi and B. Perini, Acta Crystallographica Section A: Crystal Physics, Diffraction,

Theoretical and General Crystallography, 1977, 33, 216-218. [S2] A. Kitaigorodsky, Molecular crystals and molecules, Vol. 29, Elsevier, 2012. [S3] B. Glettner, F. Liu, X. Zeng, M. Prehm, U. Baumeister, G. Ungar and C. Tschierske, Angew.

COOCH3

O

OOHOHO OH

OH

C4F9

S33

Chem. Int. Ed. 2008, 47, 6080-6083.

[S4] S. P. Verevkin, D. H. Zaitsau, V. N. Emel'yanenko and A. A. Zhabina, Fluid Phase Equilibria 2015, 397, 87-94.

[S5] A.S.N. Murthy and C.N.R. Rao, Applied Spectroscopy Reviews, 1968, 2(1), 69-191. [S6] O. Dorosh, E. Bialkowska-Jaworska, Z. Kislel, L. Pszczolkowski,. Journal of Molecular

Spectroscopy, 2007, 246, 228-232. [S7] R. Vargas, J. Garza, R. A. Friesner, H. Stern, B. P. Hay and D. A. Dixon, J. Phys. Chem. A,

2001, 105, 4963-4968. [S8] J. Y. Le Questel, M. Berthelot and C. Laurence, Journal of Physical Organic Chemistry, 2000,

13, 347-358. [S9] D. R. Borst, T. M. Korter and D. W. Pratt, Chemical Physics Letters 2001, 350, 485-490. [S10] F. H. Allen, C. A. Baalham, J. P. M. Lommerse, P. R. Raithby and E. Sparr, Acta Cryst. 1997,

B53, 1017-1024. [S11] M. Daszkiewicz, CrystEngComm, 2013, 15, 10427-10430. [S12] T. Shikata, Y. Sakai and J. Watanabe, AIP Advances 2014, 4, 067130. [S13] P. J. Tonge, R. Fausto, P.R. Carey, Journal of Molecular Structure, 1996, 379, 135-142. [S14] E. Galbiati, M. D. Zoppo, G. Tieghi and G. Zerbi, Polymer, 1993, 34, 1806-1810. [S15] G. Johansson, V. Percec, G. Ungar and J. P. Zhou, Macromolecules 1996, 29, 646-660. [S16] C. Wang, J. Y. Dong, Y. M. Zhang, F. Wang, H. P. Gao, P. F. Li, S. C. Wang and J. Zhang,

MedChemComm 2013, 4, 1434-1438. [S17] (a) K. Sonogashira, Y. Tohda and N. Hagihara, Tetrahedron Lett. 1975, 16, 4467-4470; (b) L.

Wang, J. Yan, Z. M. Tang, Q. Xiao, Y. G. Ma and J. Pei, J. Am. Chem. Soc. 2008,130, 9952-9962; (c) J. L. Wang, Z. M. Tang, Q. Xiao, Q. F. Zhou, Y. G. Ma and J. Pei, Org. Lett. 2008, 10, 17-20.

[S18] X. P. Tan, L. Y. Kong, H. Dai, X. H. Cheng, F. Liu and C. Tschierske, Chem. Eur. J. 2013, 19, 16303-16313.